JPH068366B2 - Rubber composition for tires - Google Patents
Rubber composition for tiresInfo
- Publication number
- JPH068366B2 JPH068366B2 JP63031864A JP3186488A JPH068366B2 JP H068366 B2 JPH068366 B2 JP H068366B2 JP 63031864 A JP63031864 A JP 63031864A JP 3186488 A JP3186488 A JP 3186488A JP H068366 B2 JPH068366 B2 JP H068366B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- carbon black
- rubber
- parts
- acidic groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はタイヤ用ゴム組成物に関するものであり、更に
詳しくは発熱性および高温での補強性の改良されたタイ
ヤ用ゴム組成物に関するものである。TECHNICAL FIELD The present invention relates to a rubber composition for tires, and more particularly to a rubber composition for tires having improved heat buildup and reinforcement at high temperatures. is there.
（従来の技術） タイヤおよび種々のゴム製品に使用されるゴム組成物に
おいて発熱性と補強性の同時改良を図る試みは従来より
色々と検討がなされている。(Prior Art) Various attempts have been made in the past to attempt to simultaneously improve heat generation and reinforcement in rubber compositions used for tires and various rubber products.
例えば、本件出願人が先に出願した特開昭62-18446号公
報では、低温プラズマ処理によりカーボンブラック表面
に導入される−COOH基の如き強酸性の生成を抑制し、主
に−OH基を優先的に生成させることでカーボンブラック
の分散性が改良され、これによりゴム組成物の耐発熱性
および補強性が向上し得ることが開示されている。For example, in the Japanese Patent Application Laid-Open No. 62-18446 filed by the applicant of the present application, the generation of strong acidity such as -COOH group introduced on the surface of carbon black by low-temperature plasma treatment is suppressed, and mainly -OH group is added. It is disclosed that the preferential formation of carbon black improves the dispersibility of carbon black, which can improve the heat resistance and reinforcing properties of the rubber composition.
一方、特開昭50-88150号公報には天然ゴムと合成ゴムの
混合物中に所定量の活性珪酸充填剤およびビス（アルコ
キシシリルアルキル）−オリゴスルフィドの少なくとも
１種を場合により、ゴム成分100部に対して0.1〜50部の
カーボンブラックと併用・混合することが示されてい
る。同様に特開昭61-287802号公報には、天然ゴムとス
チレン−ブタジエンゴムとを併用するゴム組成物に対し
て、ヨウ素吸着法により測定した比表面積(IA)が100mg/
g以上のカーボンブラック30〜50部と、シリカ５〜30部
と、一般式 (OR)3SiCnH2nSmH2nSi(OR)3または (OR)3SiCnH2nX（これら式中のＲはアルキル基、Ｘはメ
ルカプト基、アミノ基またはエポキシ基、ｎ，ｍは夫々
正の整数を示す）で表わされるシランカップリング剤0.
5〜６部と、所定量の軟化剤とを含むゴム組成物をキャ
ップ／ベース構造の２層トレッド構造タイヤのベースゴ
ムに適用することにより、耐カット性に優れかつ発熱性
の少ないタイヤを提供する技術が開示されている。On the other hand, JP-A-50-88150 discloses that, in a mixture of natural rubber and synthetic rubber, a predetermined amount of an active silicic acid filler and at least one kind of bis (alkoxysilylalkyl) -oligosulfide may be added, and the rubber component may be 100 parts. On the other hand, it is shown to be used and mixed with 0.1 to 50 parts of carbon black. Similarly, in JP-A-61-287802, the specific surface area (IA) measured by iodine adsorption method is 100 mg / for a rubber composition in which natural rubber and styrene-butadiene rubber are used in combination.
30 to 50 parts of carbon black of g or more, 5 to 30 parts of silica, and the general formula (OR) 3 SiCnH 2 nSmH 2 nSi (OR) 3 or (OR) 3 SiCnH 2 nX (R in these formulas is an alkyl group. , X is a mercapto group, an amino group or an epoxy group, and n and m each represent a positive integer).
By applying a rubber composition containing 5 to 6 parts and a predetermined amount of a softening agent to a base rubber of a two-layer tread structure tire having a cap / base structure, a tire having excellent cut resistance and less heat generation is provided. Techniques for doing so are disclosed.
また、特開昭61-291659号公報では導電性カーボンブラ
ックを溶媒中でシリコン化合物にて処理し、動的熱安定
性を向上させた改質カーボンブラックが、また特開昭62
-197429号公報ではポリブタジエン100重量部に対して
(a)導電性カーボンブラック10〜50重量部と(b)有機シラ
ンカップリング剤および／またはイミダゾール系化合物
0.5〜５重量部とを配合した導電性収縮フィルム用組成
物が夫々開示されている。Further, JP-A-61-291659 discloses a modified carbon black obtained by treating a conductive carbon black with a silicon compound in a solvent to improve dynamic thermal stability.
-197429 gazette is based on 100 parts by weight of polybutadiene
(a) 10 to 50 parts by weight of conductive carbon black and (b) organic silane coupling agent and / or imidazole compound
A composition for a conductive shrinkable film containing 0.5 to 5 parts by weight is disclosed, respectively.
（発明が解決しようとする問題点） しかしながら前記先行技術を、本発明の目的とする耐発
熱性および補強性の同時大幅向上という観点からみた場
合、尚不十分であるといわざるを得ない。(Problems to be Solved by the Invention) However, it cannot be said that the above-mentioned prior art is still inadequate when viewed from the viewpoint of simultaneously greatly improving the heat resistance and the reinforcing property which are the objects of the present invention.
すなわち、前記特開昭62-18446号公報記載の技術は、低
温プラズマ処理でカーボンブラック表面に−OH基を優先
的に生成させカーボンブラックの分散性を向上させるこ
とでゴム組成物の発熱性と補強性の両立を試みている
が、このものはカーボンブラックの表面が変性されてお
り活性状態にあってもゴムポリマーとの相互作用が十分
でなく、従って使用条件が苛酷なタイヤ用ゴム組成物と
して使用した場合、特に高温での補強性の面で実用上不
十分な点がみられた。That is, the technique described in JP-A-62-18446, the heat generation of the rubber composition by improving the dispersibility of the carbon black by preferentially forming -OH groups on the carbon black surface by low temperature plasma treatment. Although trying to achieve both reinforcing properties, this is a rubber composition for tires in which the surface of carbon black is modified and interaction with the rubber polymer is not sufficient even in the active state, and therefore the operating conditions are severe. When used as, it was found to be practically insufficient in terms of reinforcing property especially at high temperature.
一方、前記特開昭50-88150号公報および特開昭61-28780
2号公報記載の技術は、シリカとシランカップリング剤
に更に補強性カーボンブラックを併用・混合したゴム組
成物であるが、これらのものは共通して、シランカップ
リング剤を混合するかあるいはこれでカーボンブラック
を変性してもシランカップリング剤とカーボンブラック
との化学的結合が十分に行われにくく、カーボンブラッ
クとシランを介してのゴムポリマー同士の結合が十分に
され得ない。その結果、特に高温での引張強度の面と発
熱性（tan δ）の面でタイヤ用ゴム組成物として実用
上十分満足し得るレベルまで到達しているとはみられな
かった。従ってこれら技術には、高温での補強性が要求
されるような高性能タイヤ部材への適用を考えた場合に
は自ずと限界があった。On the other hand, JP-A-50-88150 and JP-A-61-28780 described above.
The technique described in Japanese Patent Publication No. 2 is a rubber composition in which silica and a silane coupling agent are further used in combination with and mixed with a reinforcing carbon black. Even if the carbon black is modified with, the chemical bond between the silane coupling agent and the carbon black is not sufficiently performed, and the bond between the rubber polymers via the carbon black and the silane cannot be sufficiently achieved. As a result, it did not seem that the rubber composition for tires has reached a practically satisfactory level in terms of tensile strength at high temperature and heat generation (tan δ). Therefore, these technologies naturally have limitations when considering their application to high-performance tire members that require reinforcement at high temperatures.
そこで本発明の目的は、上記問題点を解消し、発熱性お
よび高温での補強性に極めて優れたタイヤ用ゴム組成物
を提供することにある。Therefore, an object of the present invention is to solve the above-mentioned problems and to provide a rubber composition for a tire, which is extremely excellent in exothermic property and reinforcing property at high temperature.
（問題点を解決するための手段） 本発明者等は、上記問題点を解消し、タイヤ用ゴム組成
物に要求される補強性と発熱性を両立し、更にこれら特
性を実用上の効果が得られるまで高めるべくカーボンブ
ラックの表面活性状態に注目して鋭意検討を重ねた結
果、表面に適度の−OH基が存在するカーボンブラックと
シランカップリング剤とを所定量ゴム組成物に配合する
ことにより、カーボンブラック表面でシランカップリン
グ剤との相乗作用が認められ、この結果実用上極めて優
れた効果が得られることを見い出し、本発明を完成する
に至った。(Means for Solving Problems) The inventors of the present invention have solved the above problems and have both the reinforcing property and the heat generating property required for a rubber composition for a tire, and further, these properties have practical effects. As a result of repeated intensive studies paying attention to the surface active state of carbon black in order to raise it until it is obtained, it is necessary to compound a predetermined amount of carbon black and a silane coupling agent having a proper -OH group on the surface into a rubber composition. As a result, it was found that a synergistic effect with the silane coupling agent was recognized on the surface of carbon black, and as a result, an extremely excellent effect was obtained in practical use, and the present invention was completed.
すなわち本発明は、天然ゴム、ジエン系合成ゴムおよび
これらの混合物よりなる群から選ばれたゴム成分100重
量部に対して、窒素吸着法により測定した比表面積（N2
SA）が70〜250m2/gでジブチルフタレート吸油量（DBP吸
油量）が80〜150mｌ／100gの範囲内のカーボンブラック
であって、該カーボンブラック表面に導入された全酸性
基の濃度が0.25〜2.0μeq/m2、全酸性基中の弱酸性基の
割合が少なくとも65％であり、PH値が３〜5.5の範囲内
の補強性カーボンブラック30〜150重量部と、次の一般
式(1)および(2)： Ｙ3−Si−CnH2nSmCnH2nSi−Ｙ3または Ｙ3−SiCnH2nX・・・・(1) （式中のＸはニトロソ基、メルカプト基、アミノ基、エ
ポキシ基、ビニル基、塩素原子、イミド基、Ｙは炭素数
１〜４個のアルキル基またはアルコキシル基、あるいは
塩素原子、ｎおよびｍは夫々１〜６の整数を示す） Y3SiCnH2nSmX′・・・・(2) 前記のものと同じものを示す） で表わされる化合物から成る群から選択されたシランカ
ップリング剤の少なくとも１種を4.65×１０-5ｍ・ｓ〜
4.65×１０-3ｍ・ｓ（ｍはカーボンブラックの添加重量
部数、ｓはカーボンブラックのN2SA値を示す）の範囲内
で添加・混合したことを特徴とするタイヤ用ゴム組成物
に関するものである。That is, the present invention relates to a specific surface area (N 2 measured by a nitrogen adsorption method) with respect to 100 parts by weight of a rubber component selected from the group consisting of natural rubber, diene-based synthetic rubber and a mixture thereof.
SA) is 70 to 250 m 2 / g and dibutyl phthalate oil absorption (DBP oil absorption) is in the range of 80 to 150 ml / 100 g, and the concentration of all acidic groups introduced on the carbon black surface is 0.25. ~ 2.0 μeq / m 2 , the proportion of weakly acidic groups in all acidic groups is at least 65%, and the PH value is in the range of 3 to 5.5, 30 to 150 parts by weight of the reinforcing carbon black, and the following general formula ( 1) and (2): Y 3 -Si- CnH 2 nSmCnH 2 nSi-Y 3 or Y 3 -SiCnH 2 nX ···· (1 ) (X in the formula is a nitroso group, a mercapto group, an amino group, an epoxy Group, vinyl group, chlorine atom, imide group, Y is an alkyl group or alkoxyl group having 1 to 4 carbon atoms, or chlorine atom, n and m are each an integer of 1 to 6) Y 3 SiCnH 2 nSmX ′ · ... (2) The same as those described above), and at least one silane coupling agent selected from the group consisting of compounds represented by the formula: 4.65 × 10 −5 m · s
A rubber composition for a tire, which is added and mixed within a range of 4.65 × 10 −3 m · s (m is the number of parts by weight of carbon black added, and s is the N 2 SA value of carbon black). Is.
本発明において使用することのできるジエン系合成ゴム
としては、合成イソプレンゴム、スチレン−ブタジエン
ゴム、ブタジエンゴム、ブチルゴム、エチレン−プロピ
レンゴム、クロロプレンゴムおよびニトリルゴム等があ
る。Examples of the diene-based synthetic rubber that can be used in the present invention include synthetic isoprene rubber, styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, chloroprene rubber and nitrile rubber.
また、表面に−OH基の導入されたカーボンブラックは、
例えば前記特開昭62-18446号公報において本件出願人が
提示した真空低温プラズマ処理法やオゾン等を用いる化
学処理法で変性処理することにより得られる。In addition, carbon black introduced with -OH groups on the surface,
For example, it can be obtained by a modification treatment by the vacuum low temperature plasma treatment method proposed by the applicant of the present invention in JP-A-62-18446 or a chemical treatment method using ozone or the like.
かかるカーボンブラックと併用するシランカップリング
剤の添加量は、前述の如くカーボンブラックの添加量と
の関係で特定され、好ましくは1.16×１０-4ｍ・ｓ〜1.
16×１０-3ｍ・ｓの範囲内である。また、本発明のゴム
組成物にシリカを添加する場合には、シランカップリン
グ剤の添加量はシリカの添加量によっても規制され、0.
05ｍ′〜0.2ｍ′（ｍ′はシリカの添加重量部数を示
す）の関係を満足することが必要となる。The addition amount of the silane coupling agent used in combination with such carbon black is specified in relation to the addition amount of carbon black as described above, and preferably 1.16 × 10 −4 m · s to 1.
It is within the range of 16 × 10 −3 m · s. Further, when adding silica to the rubber composition of the present invention, the addition amount of the silane coupling agent is also regulated by the addition amount of silica, 0.
It is necessary to satisfy the relationship of 05 m'to 0.2 m '(m' indicates the number of parts by weight of silica added).
尚、カーボンブラックをシランカップリング剤と併用す
る際に、−OH基を導入すべく表面処理されたカーボンブ
ラックをシランカップリング剤で予め変性処理してもよ
い。この場合のシランカップリング剤による変性処理方
法としては、ヘンシエルミキサーを用い室温乃至80℃
の温度雰囲気中でカーボンブラックとシランカップリン
グ剤とを５〜20分間混合攪拌する方法と、シランカッ
プリング剤を含んだメタノール溶液中に酸化処理カーボ
ンを入れ、室温乃至80℃の温度雰囲気中で５〜20分間混
合攪拌する方法とがある。When carbon black is used in combination with the silane coupling agent, the surface-treated carbon black for introducing —OH groups may be modified beforehand with the silane coupling agent. In this case, the modification treatment method with the silane coupling agent is a room temperature to 80 ° C using a Henschel mixer.
The method of mixing and stirring carbon black and the silane coupling agent in the temperature atmosphere of 5 to 20 minutes, and the oxidation-treated carbon is put in a methanol solution containing the silane coupling agent, and the temperature is from room temperature to 80 ° C. There is a method of mixing and stirring for 5 to 20 minutes.
本発明のゴム組成物には加硫剤の硫黄、加硫促進剤、老
化防止剤、軟化剤あるいは充填剤等を適宜配合すること
ができるのは勿論のことである。It goes without saying that the rubber composition of the present invention can appropriately contain sulfur as a vulcanizing agent, a vulcanization accelerator, an antioxidant, a softening agent, a filler and the like.
尚、本発明におけるＮ2SAの測定はASTM D3037により、
またDBP吸油量の測定はASTM D3493に準拠して行った。The measurement of N 2 SA in the present invention is according to ASTM D3037.
The DBP oil absorption was measured according to ASTM D3493.
（作用） 本発明のゴム組成物に配合する補強性カーボンブラック
は、Ｎ2SAが70〜250m2/gでDBP吸油量が80〜150ml／100g
の範囲内であること要求されるが、これはこのＮ2SA値
およびDBP吸油量が夫々の下限値より小さい場合には分
散性改良効果が小さく、また上限を超える場合にも分散
性が悪く、発熱性が増大するからである。(Function) The reinforcing carbon black compounded in the rubber composition of the present invention has N 2 SA of 70 to 250 m 2 / g and DBP oil absorption of 80 to 150 ml / 100 g.
However, when the N 2 SA value and the DBP oil absorption are smaller than the respective lower limits, the effect of improving dispersibility is small, and when the upper limit is exceeded, the dispersibility is poor. This is because the exothermicity increases.
また本発明では、かかるカーボンブラックの表面に導入
される全酸性基の濃度が0.25〜2.0μeq/m2で全酸性基の
中の弱酸性基の割合が少なくとも65％の範囲内と規定す
るが、これはこの下限値未満では高温時の引張強度が低
下し、また上限を超えると破断伸びが低下して破壊特性
が低下し好ましくないからである。好ましくは、全酸性
基の濃度は0.3〜0.8μeq/m2で全酸性基の中の弱酸性基
の割合が少なくとも65％の範囲内とする。更に本発明で
は、−OH基導入によるPH値を３〜5.5の範囲内と規定す
るが、これはPH値が３未満では加硫が遅れ好ましくな
く、一方5.5を超えると−OH基が減少して本発明の目的
を達成することができなくなるからである。Further, in the present invention, the concentration of the total acidic groups to be introduced on the surface of such carbon black is 0.25 to 2.0 μeq / m 2 and the ratio of the weak acidic groups in all the acidic groups is defined to be at least 65%. This is because if it is less than the lower limit, the tensile strength at high temperature is lowered, and if it exceeds the upper limit, the elongation at break is lowered and the fracture property is lowered, which is not preferable. Preferably, the concentration of all acidic groups is 0.3 to 0.8 μeq / m 2 and the ratio of weakly acidic groups in all acidic groups is at least 65%. Further, in the present invention, the PH value due to the introduction of --OH group is defined to be in the range of 3 to 5.5. However, when the PH value is less than 3, vulcanization is delayed, which is not preferable, while when it exceeds 5.5, the --OH group decreases. Therefore, the object of the present invention cannot be achieved.
以上述べてきた特性を有するカーボンブラックの添加量
はゴム成分100重量部に対し30〜150重量部の範囲内とす
るわけだが、これは30重量部未満ではゴム組成物に対し
補強効果が十分でなく、一方150重量部を超えるとゴム
に対する分散性が悪くなり好ましくないからである。好
ましくは、かかるカーボンブラックの添加量を40〜100
重量部の範囲内とする。またシリカ併用の場合にはシリ
カの添加量は40重量部が限度であり、これを超えてシリ
カを添加すると耐摩耗性、高温破壊性が低下するため好
ましくない。尚、本発明ではシリカを添加しなくとも効
果が発揮される。The addition amount of carbon black having the characteristics described above is in the range of 30 to 150 parts by weight with respect to 100 parts by weight of the rubber component, but if this is less than 30 parts by weight, the reinforcing effect on the rubber composition is sufficient. On the other hand, if it exceeds 150 parts by weight, the dispersibility in rubber deteriorates, which is not preferable. Preferably, the amount of such carbon black added is 40 to 100.
Within the range of parts by weight. When silica is used in combination, the amount of silica added is limited to 40 parts by weight, and addition of silica in excess of this lowers wear resistance and high temperature destructiveness, which is not preferable. In the present invention, the effect is exhibited without adding silica.
次に、本発明のゴム組成物に配合するシランカップリン
グ剤の添加量は、上述の如くカーボンブラックの添加量
によっても特定され、必要に応じてシリカを添加する場
合にはシリカの添加量によっても特定されることになる
が、かかる添加量が4.65×１０-5ｍ・ｓ未満ではカップ
リング効果が極めて小さいために発熱性の改良効果が見
られず、一方4.65×１０-3ｍ・ｓを超えると補強性が低
下して好ましくない。好ましくは、シランカップリング
剤の添加量を1.16×１０-4ｍ・ｓ〜1.16×１０-3ｍ・ｓ
の範囲内とする。Next, the addition amount of the silane coupling agent to be added to the rubber composition of the present invention is specified by the addition amount of carbon black as described above, and when silica is added as necessary, it is determined by the addition amount of silica. However, if the addition amount is less than 4.65 × 10 −5 m · s, the effect of improving heat generation is not seen because the coupling effect is extremely small, while on the other hand, 4.65 × 10 −3 m · s. When it exceeds, the reinforcing property is lowered, which is not preferable. Preferably, the addition amount of the silane coupling agent is 1.16 × 10 −4 m · s to 1.16 × 10 −3 m · s.
Within the range of.
表面に−OH基導入処理が施されたカーボンブラックとシ
ランカップリング剤とを混合・添加する上記配合処法は
従来全く知られておらず、本発明において初めて行われ
たものである。本発明の構成とすることで補強性と発熱
性の大幅な改良効果がみられるのは、−OH基導入処理が
施されて分散性が改良された活性カーボンブラックとシ
ランカップリング剤との間に化学的に強固な一次結合が
形成され、更にこのシランカップリング剤がゴムポリマ
ーとの間で相互作用してカーボンブラック−シランカッ
プリング剤−ゴムポリマー間が全体的に高温にも強い結
合を形成するからである。The above-mentioned compounding method of mixing and adding a carbon black having a —OH group-introducing treatment on its surface and a silane coupling agent has not been known at all, and is the first to be carried out in the present invention. By the constitution of the present invention, a significant improvement effect on the reinforcing property and the exothermic property can be seen between the activated carbon black and the silane coupling agent, which have been subjected to the -OH group introduction treatment to improve the dispersibility. A chemically strong primary bond is formed in the polymer, and this silane coupling agent interacts with the rubber polymer to form a strong bond between the carbon black, the silane coupling agent, and the rubber polymer as a whole at high temperatures. Because it is formed.
（実施例） 次に本発明を実施例により説明する。(Examples) Next, the present invention will be described by examples.
先ずは、真空低温プラズマ処理したカーボンブラックを
用いて試作した各種試験ゴム組成物について行った物性
試験について説明する。First, the physical property tests carried out on various test rubber compositions prepared by using carbon black subjected to vacuum low temperature plasma treatment will be described.
真空低温プラズマ処理 500mlのパイレックス製フラスコ型プラズマチャンバー
内にカーボンブラック50gを入れ、処理を均一にし灰化
を抑制するために少なくとも５rpm以上でフラスコを回
転させながら真空低温プラズマ処理を行った。Vacuum low temperature plasma treatment 50 g of carbon black was placed in a 500 ml Pyrex flask type plasma chamber, and vacuum low temperature plasma treatment was performed while rotating the flask at least 5 rpm or more in order to make the treatment uniform and suppress ashing.
この真空低温プラズマ処理は、高周波出力（13.56MHz）
25Ｗ、真空度0.3Torrおよび処理ガス流量50ml／minの条
件下、次の第１表に示す処理ガスおよび処理時間にて行
った。This vacuum low temperature plasma processing is high frequency output (13.56MHz)
The processing gas and the processing time shown in the following Table 1 were performed under the conditions of 25 W, a vacuum degree of 0.3 Torr and a processing gas flow rate of 50 ml / min.
かかる処理により各カーボンブラックの表面に導入され
た−OH基の濃度およびpH値は以下のようにして測定し
た。The concentration and pH value of the —OH group introduced on the surface of each carbon black by such treatment were measured as follows.
−OH基の濃度測定 カーボンブラック表面の−OH基の濃度はH.P.Boehmの方
法（Angew.Chem.internat.Edit.,５，533(1966)および
同，３，669(1964))に従い、表面−OH基を炭酸水素ナト
リウム、水酸化ナトリウムにより中和することにより求
めた。-OH group concentration measurement -OH group concentration on the surface of carbon black was measured according to the method of HP Boehm (Angew.Chem.internat.Edit., 5 , 533 (1966) and 3 , 669 (1964)). It was determined by neutralizing the group with sodium hydrogen carbonate and sodium hydroxide.
pH値の測定 試料１ｇをイオン交換水100ml中に添加して15分間煮沸
し、48時間放置した後、スターラでかき混ぜ乍ら懸濁液
のpH値をpHメーターで測定した。Measurement of pH value 1 g of a sample was added to 100 ml of ion-exchanged water, boiled for 15 minutes, allowed to stand for 48 hours, and then stirred with a stirrer to measure the pH value of the suspension with a pH meter.
表面−OH基の濃度およびpH値の測定結果を第１表に併記
する。The measurement results of the surface-OH group concentration and pH value are also shown in Table 1.
上述の如く処理した第１表に示す各種カーボンブラック
を、下記の第２表に示すシランカップリング剤と共に以
下の第３表に示し配合割合（重量部）でゴム成分等と配
合して、各種試験ゴム組成物を作成した。 The various carbon blacks shown in Table 1 treated as described above were mixed with the rubber component and the like at the blending ratio (parts by weight) shown in Table 3 below together with the silane coupling agent shown in Table 2 below to obtain various types. A test rubber composition was prepared.
これら試験ゴム組成物につき、以下に示す引張強度、モ
ジュラスおよび発熱性としてtan δを測定した。For these test rubber compositions, tan δ was measured as the tensile strength, modulus and exothermicity shown below.
引張強度 JIS K6301に準じて100℃にて測定した。Tensile strength Measured at 100 ° C according to JIS K6301.
モジュラス JIS K6301に準じて100℃にて300％伸長時の引張応力を
測定した。The tensile stress at 300% elongation was measured at 100 ° C according to the modulus JIS K6301.
tan δ レオメトリックス社製メカニカルスペクトロメーターを
用いて、動的剪断歪振幅1.0％、振動1.0Hzおよび測定温
度30℃にて測定した。値が小さい程分散性は良好であ
る。The measurement was performed using a tan δ Rheometrics mechanical spectrometer at a dynamic shear strain amplitude of 1.0%, a vibration of 1.0 Hz, and a measurement temperature of 30 ° C. The smaller the value, the better the dispersibility.
引張強度、モジュラスおよびtan δの測定結果を第３
表に併記する。The tensile strength, modulus and tan δ measurement results are
Also listed in the table.
次に、下記に示す酸化処理したカーボンブラックを用い
て、前述のようにして物性試験を行った。 Next, a physical property test was performed as described above using the carbon black subjected to the oxidation treatment shown below.
カーボンブラックの酸化処理１ ISAF級カーボンブラック（商品名 旭＃80，旭カーボン
（株）製；窒素吸着比表面積117m2/g，ジブチルフタレ
ート吸油量115ml／100g）（下記の第４表に示すISAFカ
ーボンＡ）100gを１に過酸化水素２ｇを含む水溶液に
加え、60〜70℃に加熱して攪拌しながら30分間反応させ
た。反応完了後のカーボンブラック懸濁液を濾過し、次
に乾燥機内120℃で12時間乾燥させて酸化処理カーボン
ブラックを調製した（ISAFカーボンＣ）。酸化処理され
たカーボンブラックは全酸性基が0.34μeq/m2、弱酸性
基が0.28μeq/m2で弱酸性基の割合が82％という特性を
有していた。Oxidation treatment of carbon black 1 ISAF grade carbon black (trade name Asahi # 80, manufactured by Asahi Carbon Co., Ltd .; nitrogen adsorption specific surface area 117 m 2 / g, dibutyl phthalate oil absorption 115 ml / 100 g) (ISAF shown in Table 4 below) 100 g of carbon A) was added to an aqueous solution containing 2 g of hydrogen peroxide in 1 and heated to 60 to 70 ° C. and reacted for 30 minutes while stirring. The carbon black suspension after completion of the reaction was filtered and then dried in a dryer at 120 ° C. for 12 hours to prepare an oxidation-treated carbon black (ISAF carbon C). The oxidized carbon black had the characteristics that the total acidic groups were 0.34 μeq / m 2 , the weak acidic groups were 0.28 μeq / m 2 , and the ratio of weak acidic groups was 82%.
また、過酸化水素の量を0.1g，5.0g，20.0g，30.0gと変
量させ酸化状態の異なるカーボンブラックを同様の操作
により調製した（IDAFカーボンＢ，Ｄ〜Ｆ）。Further, carbon blacks having different oxidation states were prepared by varying the amount of hydrogen peroxide to 0.1 g, 5.0 g, 20.0 g and 30.0 g (IDAF carbons B, DF).
更に、HAF級カーボンブラック（HAFカーボンＪ）を過酸
化水素の量5.0gにて上記と同様の処理を施し、酸化処理
HAFカーボンブラックを調製した（HAFカーボンＫ）。Furthermore, HAF carbon black (HAF Carbon J) was treated with the same amount of hydrogen peroxide as 5.0 g, and then oxidized.
HAF carbon black was prepared (HAF carbon K).
カーボンブラックの酸化処理２ 酸化処理１で使用したカーボンブラックを用い、過酸化
水素に替えて、１％の硝酸水溶液で処理した（ISAFカー
ボンＧ）。Oxidation Treatment 2 of Carbon Black The carbon black used in Oxidation Treatment 1 was replaced with hydrogen peroxide and treated with a 1% nitric acid aqueous solution (ISAF Carbon G).
カーボンブラックの酸化処理３ 酸化処理１で使用したカーボンブラック100gに対し、オ
ゾン発生装置からのオゾンを含む空気を５／minの流
量で30分間通気し、酸化処理した（ISAFカーボンＨ）。
尚、ここで使用したオゾン発生装置のオゾン発生量は、
空気を使用した場合で3.6g/hrであった。Oxidation treatment 3 of carbon black With respect to 100 g of carbon black used in the oxidation treatment 1, air containing ozone from an ozone generator was aerated for 30 minutes at a flow rate of 5 / min for oxidation treatment (ISAF carbon H).
The amount of ozone generated by the ozone generator used here is
When air was used, it was 3.6 g / hr.
上記カーボンブラックの特性試験は下記の条件に従い行
った。The characteristic test of the above carbon black was performed according to the following conditions.
全酸性基の定量 カーボンブラック１ｇを精秤し、1/250規定の水酸化ナ
トリウム溶液50mlを加え、還流冷却器を付けたフラスコ
中で100℃、２時間煮沸を行った後、その上澄液10mlを1
/500規定の塩酸で滴定した。空試験を同時に平行して行
ない両者の差から全酸性基量（μeq/g）を求め、前もっ
て測定しておいた供試カーボンブラックの窒素吸着比表
面積（N2SA）で単位表面積当りの全酸性基量（μeq/
m2）を計算した。Quantification of total acidic groups 1 g of carbon black was precisely weighed, 50 ml of 1/250 N sodium hydroxide solution was added, and the mixture was boiled at 100 ° C for 2 hours in a flask equipped with a reflux condenser, and then the supernatant was obtained. 10 ml to 1
Titrated with 500 N hydrochloric acid. The blank test was conducted in parallel at the same time, the total amount of acidic groups (μeq / g) was calculated from the difference between the two, and the nitrogen adsorption specific surface area (N 2 SA) of the sample carbon black measured in advance was used to determine the total amount per unit surface area. Amount of acidic group (μeq /
m 2 ) was calculated.
弱酸性基の定量 弱酸性基量は次式、 弱酸性基量（μeq/m2）＝全酸性基量（μeq/m2）− 強酸性基量（μeq/m2） により求めた。Quantitative weakly acidic group amount of weakly acidic groups following formulas, the amount weakly acidic groups (μeq / m 2) = total amount of acidic group amount (μeq / m 2) - was determined by strong acid group amount (μeq / m 2).
弱酸性基の定量 カーボンブラック２ｇを精秤し、1/50規定の炭酸水素ナ
トリウム溶液100mlを加え、室温で４時間振とうした
後、その上澄液20mlに1/50規定の塩酸21mlを加え、15分
間煮沸した後過剰の塩酸を1/500規定の水酸化ナトリウ
ムで滴定した。同時に空試験を並行して行い両者の差か
ら強酸性基量（μeq/g）を求め、前もって測定しておい
た供試カーボンブラックの窒素吸着比表面積（N2SA）で
単位表面積当りの強酸性基量（μeq/m2）を計算した。Quantification of weakly acidic group 2 g of carbon black was precisely weighed, 100 ml of 1/50 normal sodium hydrogen carbonate solution was added, and after shaking at room temperature for 4 hours, 21 ml of 1/50 normal hydrochloric acid was added to 20 ml of the supernatant. After boiling for 15 minutes, excess hydrochloric acid was titrated with 1 / 500N sodium hydroxide. At the same time, a blank test is performed in parallel to determine the amount of strongly acidic groups (μeq / g) from the difference between the two, and the nitrogen adsorption specific surface area (N 2 SA) of the sample carbon black measured in advance is used to determine the strong acid per unit surface area. The amount of the functional group (μeq / m 2 ) was calculated.
窒素吸着比表面積（N2SA） ASTM D3037-78に準拠した。Nitrogen adsorption specific surface area (N 2 SA) According to ASTM D3037-78.
pH ASTM D1512-75に準拠した。According to pH ASTM D1512-75.
揮発分 JISK-6221に準拠した。Volatile content Compliant with JIS K-6221.
得られた結果を第４表に示す。The results obtained are shown in Table 4.
上述の如く処理した第４表に示す各種カーボンブラック
を、上記の第２表に示すシランカップリング剤と共に以
下の第５表に示す配合割合（重量部）でゴム成分等と配
合して、各種試験ゴム組成物を作成した。配合物の加硫
条件は145℃、30分である。 The various carbon blacks shown in Table 4 treated as described above were mixed with the silane coupling agent shown in Table 2 together with the rubber component and the like at the blending ratio (parts by weight) shown in Table 5 below to obtain various types. A test rubber composition was prepared. The vulcanization conditions of the compound are 145 ° C. and 30 minutes.
これら試験ゴム組成物につき上記引張強度、モジュラス
並びに以下に示す耐摩耗性、tanδおよび反発弾性を評
価した。The tensile strength, modulus, abrasion resistance, tan δ and impact resilience shown below were evaluated for these test rubber compositions.
耐摩耗性 ランボーン摩耗試験機を用い、摩耗損失量を測定し、下
式によって算出した。Abrasion resistance The amount of abrasion loss was measured using a Lambourn abrasion tester and calculated by the following formula.
耐摩耗指数＝（比較例９の試験片の容積損失量／供試試
験片の容積損失量）×100 値が大なる程耐摩耗性は良好である。Abrasion resistance index = (volume loss amount of test piece of Comparative Example 9 / volume loss amount of test sample specimen) × 100 The larger the value, the better the abrasion resistance.
tan δ 動的粘弾性測定機（（株）岩本製作所製粘弾性スペクト
ロメーターVES-S型）を用いて、動的剪断歪振幅1.0％、
周波数50Hzおよび測定温度25℃にて測定した。値が小さ
い程発熱性が改良されている。tan δ Using a dynamic viscoelasticity measuring instrument (Viscoelasticity spectrometer VES-S type manufactured by Iwamoto Seisakusho Co., Ltd.), a dynamic shear strain amplitude of 1.0%,
It was measured at a frequency of 50 Hz and a measurement temperature of 25 ° C. The smaller the value, the better the heat buildup.
反発弾性 JIS K6300-974に準拠した。Impact resilience Compliant with JIS K6300-974.
上記物性の測定結果を第５表に併記する。The results of measuring the above physical properties are also shown in Table 5.
（発明の効果） 上記第３表および第５表に示す測定結果からも分かるよ
うに、本発明の要求を満足するように−OH基導入処理の
施されたカーボンブラックとシランカップリング剤とを
併用・混合したゴム組成物では、ジエン系ゴムのすべて
において高温での補強性と室温での発熱性（tan δ）
が同時に改良され、特に高温での引張強度面で30〜40
％、またtanδで10〜20％の効果がみられ、これは驚く
べき改良効果であるといえる。かかる改良効果は上記変
性カーボンブラックと所定量のシランカップリング剤と
の組み合わせによる相乗効果が発揮されていることの裏
付けとなるものである。 (Effects of the Invention) As can be seen from the measurement results shown in Tables 3 and 5, the carbon black subjected to the -OH group introduction treatment and the silane coupling agent so as to satisfy the requirements of the present invention were prepared. With the rubber composition used together and mixed, the reinforcing properties at high temperature and the exothermic property at room temperature (tan δ) for all diene rubbers
Is improved at the same time, especially in terms of tensile strength at high temperature 30-40
%, And an effect of 10 to 20% in tan δ was observed, which is a surprising improvement effect. Such an improving effect supports that the synergistic effect of the combination of the modified carbon black and a predetermined amount of the silane coupling agent is exerted.
Claims (1)
の混合物よりなる群から選ばれたゴム成分100重量部に
対して、窒素吸着法により測定した比表面積（N2SA）が
70〜250m2/gでジブチルフタレート吸油量（DBP吸油量）
が80〜150mｌ／100ｇの範囲内のカーボンブラックであ
って、該カーボンブラック表面に導入された全酸性基の
濃度が0.25〜2.0μeq/m2、全酸性基中の弱酸性基の割合
が少なくとも65％であり、pH値が３〜5.5の範囲内の補
強性カーボンブラック30〜150重量部と、次の一般式(1)
および(2)： Ｙ3−Si−CnH2nSmCnH2nSi−Ｙ3または Ｙ3−SiCnH2nX・・・・(1) （式内のＸはニトロソ基、メルカプト基、アミノ基、エ
ポキシ基、ビニル基、塩素原子、イミド基、Ｙは炭素数
１〜４個のアルキル基またはアルコキシル基、あるいは
塩素原子、ｎおよびｍは夫々１〜６の整数を示す） Ｙ3SiCnH2nSmX′・・・・(2) 々前記のものと同じものを示す） で表わされる化合物から成る群から選択されたシランカ
ップリング剤の少なくとも１種を4.65×１０-5ｍ・ｓ〜
4.65×１０-3ｍ・ｓ（ｍはカーボンブラックの添加重量
部数、ｓはカーボンブラックのN2SA値を示す）の範囲内
で添加・混合したことを特徴とするタイヤ用ゴム組成
物。1. A specific surface area (N 2 SA) measured by a nitrogen adsorption method with respect to 100 parts by weight of a rubber component selected from the group consisting of natural rubber, diene-based synthetic rubber and a mixture thereof.
Dibutyl phthalate oil absorption (DBP oil absorption) at 70 to 250 m 2 / g
Is in the range of 80 to 150 ml / 100 g, the concentration of all acidic groups introduced on the surface of the carbon black is 0.25 to 2.0 μeq / m 2 , and the proportion of weakly acidic groups in all the acidic groups is at least 65% and 30 to 150 parts by weight of reinforcing carbon black having a pH value of 3 to 5.5 and the following general formula (1)
And (2): Y 3 -Si- CnH 2n SmCnH 2 nSi-Y 3 or Y 3 -SiCnH 2 nX ···· (1 ) ( the expression of X is a nitroso group, a mercapto group, an amino group, an epoxy group, Vinyl group, chlorine atom, imide group, Y is an alkyl group or alkoxyl group having 1 to 4 carbon atoms, or chlorine atom, n and m are each an integer of 1 to 6) Y 3 SiCnH 2 nSmX ′ ...・ (2) Each of which has the same meaning as the above), and at least one silane coupling agent selected from the group consisting of compounds represented by the following formula: 4.65 × 10 −5 m · s
A rubber composition for a tire, which is added and mixed within a range of 4.65 × 10 −3 m · s (m is the number of parts by weight of carbon black added, and s is the N 2 SA value of carbon black).
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63031864A JPH068366B2 (en) | 1987-04-23 | 1988-02-16 | Rubber composition for tires |
| DE3813678A DE3813678A1 (en) | 1987-04-23 | 1988-04-22 | RUBBER MIX FOR TIRES |
| US07/185,745 US4820751A (en) | 1987-04-23 | 1988-04-25 | Rubber composition for tires |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62-98501 | 1987-04-23 | ||
| JP9850187 | 1987-04-23 | ||
| JP63031864A JPH068366B2 (en) | 1987-04-23 | 1988-02-16 | Rubber composition for tires |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6420246A JPS6420246A (en) | 1989-01-24 |
| JPH068366B2 true JPH068366B2 (en) | 1994-02-02 |
Family
ID=26370384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63031864A Expired - Fee Related JPH068366B2 (en) | 1987-04-23 | 1988-02-16 | Rubber composition for tires |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4820751A (en) |
| JP (1) | JPH068366B2 (en) |
| DE (1) | DE3813678A1 (en) |
Families Citing this family (148)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01207359A (en) * | 1988-02-16 | 1989-08-21 | Asahi Carbon Kk | Carbon black having modified surface for blending in tread rubber |
| JPH0641539B2 (en) * | 1988-07-21 | 1994-06-01 | 東海カーボン株式会社 | Carbon black for tire tread rubber compounding |
| JP2708063B2 (en) * | 1988-11-28 | 1998-02-04 | サンスター技研株式会社 | Primer composition for glass |
| JPH06102737B2 (en) * | 1989-04-13 | 1994-12-14 | 東洋ゴム工業株式会社 | Tread rubber composition for tire |
| US5230878A (en) * | 1989-10-02 | 1993-07-27 | Tokai Carbon Co., Ltd. | Carbon black for tire tread rubber |
| ES2085959T5 (en) * | 1990-03-02 | 2001-02-01 | Bridgestone Corp | TIRES |
| IT1242480B (en) * | 1990-03-23 | 1994-03-17 | Pirelli | ELASTOMERIC COMPOSITION FOR TIRES OF POLYCHLOROPRENE OR BUTYL RUBBER, CHLORINATED OR BROMURATED TIRES. |
| GB9013369D0 (en) * | 1990-06-15 | 1990-08-08 | Sumitomo Rubber Ind | Tyre tread compound |
| DE4119959A1 (en) * | 1991-06-18 | 1992-12-24 | Degussa | METHOD FOR PRODUCING VULCANIZABLE, RUSSELED PLASTIC AND RUBBER MIXTURES |
| US5248722A (en) * | 1992-06-02 | 1993-09-28 | Bridgestone Corporation | Tire tread composition |
| NO309773B1 (en) * | 1993-09-01 | 2001-03-26 | Sumitomo Rubber Ind | Rubber material for tread on tires, as well as car tires that have such a tread |
| GB9318850D0 (en) * | 1993-09-11 | 1993-10-27 | Sumitomo Rubber Ind | Rubber compositions |
| WO1995017458A1 (en) * | 1993-12-20 | 1995-06-29 | Ppg Industries, Inc. | Tire tread composition comprising highly reinforcing silica |
| WO1995017459A1 (en) * | 1993-12-20 | 1995-06-29 | Ppg Industries, Inc. | Tire tread composition comprising highly reinforcing silica |
| EP0676443B1 (en) * | 1994-04-06 | 2003-03-05 | Bayer Inc. | Silica filled rubbery vulcanizates |
| US5494955A (en) * | 1994-04-08 | 1996-02-27 | Columbian Chemicals Company | Use of silane coupling agent with carbon black to enhance the balance of reinforcement properties of rubber compounds |
| DE4435311A1 (en) * | 1994-10-01 | 1996-04-04 | Huels Silicone Gmbh | Reinforcement additives |
| DE59507998D1 (en) * | 1994-11-30 | 2000-04-20 | Sp Reifenwerke Gmbh | Rubber compound, tire tread made therefrom and tires with this tire tread |
| DE4442692A1 (en) * | 1994-11-30 | 1996-06-05 | Sp Reifenwerke Gmbh | Rubber mixts. for tyre running surfaces |
| US5575845A (en) * | 1994-12-15 | 1996-11-19 | Cabot Corporation | Carbon black products for coloring mineral binders |
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|---|---|---|---|---|
| US4519430A (en) * | 1982-07-29 | 1985-05-28 | The B. F. Goodrich Company | Energy saving tire with silica-rich tread |
| JPS61287802A (en) * | 1985-06-15 | 1986-12-18 | Toyo Tire & Rubber Co Ltd | Tire having good resistance to cutting |
| JPS61291659A (en) * | 1985-06-19 | 1986-12-22 | Kyowa Yuka Kk | Method of improving carbon black |
| JPS6218446A (en) * | 1985-07-08 | 1987-01-27 | Bridgestone Corp | Rubber composition containing carbon black having improved dispersibility |
| JPS62184463A (en) * | 1986-02-10 | 1987-08-12 | Toshiba Corp | Electrophotographic sensitive body |
| JPS62197429A (en) * | 1986-02-25 | 1987-09-01 | Tokyo Ink Kk | Composition for electroconductive shrinkable film |
-
1988
- 1988-02-16 JP JP63031864A patent/JPH068366B2/en not_active Expired - Fee Related
- 1988-04-22 DE DE3813678A patent/DE3813678A1/en active Granted
- 1988-04-25 US US07/185,745 patent/US4820751A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US4820751A (en) | 1989-04-11 |
| DE3813678C2 (en) | 1990-07-19 |
| JPS6420246A (en) | 1989-01-24 |
| DE3813678A1 (en) | 1988-11-10 |
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